Manufacture of new azo dyes



x no brewing. lpplication filedykpril 7,

iii

Patented Sept. 13, 1932 PEEIA'L EMIcAL INDUSTRIES LIMITED, OF WESTMINSTER, ENeLANp mANuEAd'rUEE OF NEW Azo DYES In the specification of application Serial No. 427,961 new trisazo dyes which have the Valuable property of dyeing axregenerated cellulose rayon in even shades are obtained'by tetrazotizinga 3 i4"-diaminoazobenzene or a substitution product thereof. This latter class of compounds may. be represented by the probable formula:

wherein R, represents hydrogen, an allryl or alkoxy group, R5 represents hydrogen or an alkoxy group and X represents hydrogen or a sulphonic group, and coupling withsuitable components v 3 v V According to thepresent invention, which is an improvement on or modification, of the invention claimed in the specifieation referred to above, Ihaven found that in placeof the 3 4'-diaminoazobenzene or its derivatives there may be used 3-aminobenzeneJflazo-{l' aminonaphth lene or a nuclear substitution product thereof. The 3 -am ijnobenzene-1 -a zol aminonaphthalene or its derivatives 7 may be obtained for instanoaby coupling'a diazo: tized m nitroamine of the benzene serieswith a-naph'thylamine or a para-coupling nuclear substituted derivative thereof and reducing the nitro aminobenzenea-zonaphthalene thus obtained. It is 'not, however, a necessary part of this invention ,to isolate the nitro aminoben'zeneazonaphthalene. The, 3-nitrobenzene 1--azo-'zaminonaphthalene may, for example, be di-azotized and coupled with a phenol, naphthol or with a sulphonic acid or carboxylic acid derivative thereof, the nitro group in the resultant nitrodisazo dyestufi reduced and the amino disazo dyestufl' diazotized and coupled with a eouplingcomponent.

The trisaz o dyes thus produced may be represented by the following formula:

Ra f,

wherein R represents a benzene or naphthalene residue, R represents the coupled residue of said coupling component, R represents hydrogen an alkyl or alkoxy group, R represents'hydrogen or an alkoxy group and X represents hydrogen ora sulphonic group.

' In -my process by properly selecting the various diazo compounds andthe coupling components I may'produce certain subgeneric 1 classes of dyes within the generic. class given above, which are advantageous. Some of these subgenerieclasses may be represented by the following formulae:

017E): wherein R represents a naphthalene residue, R represents hydrogen or an alkyl group and R represents hydrogen, abenzene residue or an acyl group, and in which wis one ortwo.

RAIZETBLD BRiGHTMAN, as; Enidmir;MANCHESTER, ENGtANnnssIeiioR 'ro 1 19301831211 No. 442,452, and in Great Britain April 11, 1929.

- wherein R represents a naphthalene or benzene residue and A represents hydrogen, or a COOH or SO H group.

at least two carboxylic or sulphonic acid groups or one of each should be present in the trisazo dyestufi' molecule.

The invention is illustrated by the following-examples, to which however it is not limited. The parts are by weight.

. Eamon/pie 1.138 parts of m-nitroa-niline are diazotized with 69 parts of sodium nitrite and 250 parts of 36% hydrochloric acid and to the diazo solution there is added a solution of 143 parts of -naphthylamine in 100 parts of 36% hydrochloric acid. 280 parts .of sodium acetate are added to remove mineral acidity and the mixture is stirred until coupling is complete, when the monoazo dyestufl' is filtered off. .The. aminoazo dyestufl' is then stirred into water and diazotized with 300 parts of 36% hydrochloric acid and 69 parts of sodium nitrite, The diazo suspension is stirred into a cold solution of 138 parts of salicylic acid in 40 parts of sodium hydroxide containing 400 parts of sodium carbonate. The coupling is stirred untilco'mbination is complete when it is heated up and the nitro group in the nitrodisazo dyestufi reduced by the addition of about 360 parts of sodium sulphide crystals. After stirring until reduction ofthe nitro groups is complete the amino-disazo dyestuif is salted outwith common salt, dissolved in water and diazotized with 69 parts of sodium nitrite and 300 Example 2. 152 parts of 4-nitro2-toluidine are diazotized with parts of sodium COOH OH H; MGOH nitrite and 250 parts of 36% hydrochloric acid. To the diazo solution there is added a solution of 223 parts of Cleves acid and about 280 parts of sodium acetate crystalsto remove mineral acidity; After stirring vuntil combination is complete, the coupling is made faintly alkaline and the monoazo yestuff precipitated by the addition of common salt and filtered off. The aminoazo dyestuff is dissolved in water and diazotized with 69 parts of sodium nitrite and 300 parts of 36% hydrochloric acid. The diazo solution is stirred into a solution of 144 parts of ,B-naphthol'in 40 parts of sodium hydroxide containing 400 parts of sodium carbonate, and when combination is complete the mixture is heated up and the nitro group in the nitrodisazo dyestuff reduced with 360 parts of sodium sulphide crystals. After stirring until this reduction is complete the aminodisazo dyestufi is salted out by the addition of common salt, filtered off, dissolved in Water and diazotized with 69 parts of sodium nitrite and 300 parts of 36% hydrochloric acid. The diazo sus- 110 pension is stirred into a well-cooled solution of 319 parts of 1-amino-.8.-napht h0l2: 4 .--disulphonic acid and 400 parts of sodium carbonate. The mixture is maintained cold and alkaline and after stirringuntil coupling is complete it is heated up and the dyestuif isolated by the addition of common salt. This trisazo dye in the form of the free acid may be represented by the following formula:

. v I .114) I OaH noas I It dyes viscose rayon a blue shade.

Other examples to illustrate the invention are given in the following table.

salicylic acid l V i I Diaz'otized and coilpled Iiitrbdisazo dyeetdfi reduced to emino- Shade 61': viscose Amnqazqdyestufi i with t I disazo dyestufi and coupled'with rayon -1.4hitr0-2-anisidine4Cleves acid o-cresotinic acid 2-be%oylamino-8-napl1th0l-6-su1phonic Brown. 7

- .801 v V 2.m-nitroani1ine 01eves acid N-W- 2-amino-8-naphthol-fi-sulphonicacid Brownish-violet. 3.m-nitroaniline 2;ethoxy-Cleves acid salicylic ld 2-phe1nylami1 1o- S-naphthol -6-su.lphonic Blue.

v e I am i I LID-nitrcanilineaCleVes acid l-naphtholfi-s lphonic acid. pl ei gl -2-amin -8-naphtl1c1-6-sulpl1onic Violet black.

. acl 5.4-nitr0-2-anisidine Cleves acid l-naphtholi-sulphonic acid l-amino-8-naphthol-4-sulphonic acid Navy blue. fim-nitroaniline-Klleve's acid salicylic acid vacety-2-amino-8-ncpl1thol-fi-sl lphonic Brown. 8'01 1-emino-8-naphtho1-3:fi-disulphonic acid--. Violet.

The trisazo dyes set forth'in the abovetable may be represented by thefollowing fOIILiU;

lee; the formuIse giving the form of the free acid.

dyestu'fi in the O CH;

Instead of employing the 3-nitroben zene- V 1'-azo-4 amino-naphthalene as described I may start from 3-aminobenezene-1-azo-4 aminonaphthalene, tetrazotizing this and coupling it with two molecular proportions of components in the manner known tochem ists to obtain the same indicated. s 7

Having now particularly described and ascertained the nature of my said invention and in what manner the same is to be performed, I declare that what I claim is:

1. In the manufacture of new trisazo dyes capable of dyeing regenerated cellulose in even level shades, the process which comprises diazotizing a nitro-azo-compound having the probable formula:

dyestuffs as above wherein R represents hydrogen, an alkyl or alkoxy group, R represents hydrogen or an alkoxy group, X represents hydrogen or sulphonic group, coupling the diazo compound thus produced with an azo coupling component of the class consisting of a carbox ylic acid of a phenol, a naphthol, and a naphthol-sulfonic acid, to form a nitro-disazo' compound, reducing the said nitro disazo compound to form the corresponding amino compound, diazotizing said amino compound and coupling with an amino-naphtholsulphonic acid and then isolating the trisazo dye thus produced. s

2. In the manufacture of new trisazo dyes capable of dyeing regenerated cellulose in even level shades, the process which comprises diazotizing a nitro-azo-compound having the probable formula:

wherein R represents hydrogen, an alkyl or alkoxy group, R represents hydrogen or an alkoxy group, and X represents hydrogen or sulphonic group, coupling the diazo compound thus produced with an azo dye coupling component of the class consisting of salicylic acid, beta-naphthol, orthocresotinic acid, 1 :4-naphthol-sulphonic acid, 1: 5 naphthol-sulphonic acid, to produce a nitro disazo compound, reducing the nitro group of said nitro-disazo compound, to form the corresponding amino compound, diazotizing said amino disazo compound and wherein R represents a benzene or naphthalene residue, R represents a coupled residue of an azo dye coupllng component, R represents hydrogen, akyl or alkoxy group,

R represents hydrogen or an alkoXy group, X represents hydrogen or sulphonic group and A represents hydrogen, a (JOOH or SO H group, the process which comprises dlazotlzlng a meta-nltro benzene-1-azo-4L- amino naphthalene compound having the probable formula:

and coupling the diazo compound thuspror" duced, with an azo dye coupling component having the probable formula:

to forma nitro-diazo compound, reducing the ,nitro group of said nitro-disazo compound so as to form the corresponding amino compound, re-diazotizing said amino compound 1 and coupling with an amino-naphthoLsulphonic acid having the probable formula:

wherein m is one or two and R represents 1 hydrogen, a benzene residue or an acyl group and then isolating the trisazodyestuff thus obtained. y

4. In'the manufacture of new trisazo dyes capable of dyeing regenerated cellulose in (Ho-sub wherein R3 represents hydrogenpa "benzene Lease 1 evenlevelshadesand havin gtheprobable formula: j

residue or an acyl group, R represents hying a nitro benzene-1-azo-4-amino naphthalene compound having the probable formula: 5

having the probable formula! a H0 to form a nitroi-disazo compound, reducing the ntro group of sa d nltro-dlsazo comg pound so as'to form the corresponding amino compound, re-diazotizing said amino compound and coupling with an amino naphthol' sulphonic acid having the probable formula:

wherein mis 1 e1 2 and'R representshyd'roen 4 a benzene residue or an ac l rou and then [isolating the ft risazo dyestufi thiisob- I V a i I I wherein R rep-resents hydrogen, alkyl' or capable of. dyeingj'regenerated cellulose i in even level Shades ;lg l li i i i fonic group, '00 is 1 or 2and- A represents formula coon wherein R represents hydrogen or an alkyl g oup; R8 epre hy r g a b zene, residue or an acyl group, R5 repr n y drogen, an alkylor alkoxy group, R represents hydrogen, or an 'alkox'y group,

or SO H group, the process which comprises dlazotizing a nltro benzene-Y-azo-el'ammo [naphthalene p n having a Probable formula: a V

. x i and coupling the 'diazo compound thus pro duced, with an azo dye coupling component having the probable formula:

coon v represents hydrogen or sulphonic group, v is 1 or 2, and A represents hydrogen'a COOH to form a nitroj-disa z o"compound, reducing I the ntro group ofsa d nltro-disazo com Y then isolating tained; c

6. In the manufacture of new trisazo dyes capable of dyeing regenerated cellulose'in even level shades formula alkoxy group, R represents hydrogen or an alkoxy group,X represents hydrogen or sulhydrogen a COOH or SO H group, the process which comprises diazotizing a nitro benand coupling the diazo compound thus proand having the probabl ducedwithan azo dye coupling component having the probable formula: V

BIN

(Hols) wherein a: is 1 or 2 and then isolating the trisazo dyestufl thus obtained.

7. As new roducts, trisazo dyes having in the form of t e free acid the following struc- 5 tural formula: V F R1N=NRrN=N--B| Rr-N=N wherein R represents a benzene residue, R 80 represents a benzene or napththalene residue, 3 represents a coupled residue of an azo dye coupling component of-the class consisting of phenols, naphthols, phenol-carboxylic acids and naphthol-sulphonic acids, R represents 8&4 coupled residue of an amino-naphthol sulphonic acid of the class consisting of 1: 8-amino-naphthol-sulphonic acids, 2:'8-amino naphthol-sulphonic acid and 2-substitutedamino 8-naphthol-sulphonic acids, the azo groups attached to B, being in the meta position to each other and the azo groups attached to R being in the para position to each other, said trisazo dyes containing at least two acid groups of type COOH or so H, one of Whichis a SOJ-l group and being capable of dyeing regenerated cellulose in even level shades.

8. As new products, trisazo dyes having in the form of the free acid the following structural formula phonic acid of the class consisting of 2 8-am amino-8-naphthol-6.sulphonic acid, 2-acetylamino-S-sulphonic'. acid 1 S-aminonaphthol-2:4 disulphonic acid, 1:8-animonaphthol-3z6-disulphonic acid and 1:8-am in o naphtholl-sul honic acid, and X represents hydrogen or a r 0 H group, said trisaz'o dyes containing at least vtwo acidgroups of the type, COOH or SO H, and being capable of ino-naphthol-fi-sulphonic acid, .Z-benzOylamr ino-8-naphthol-6-sulphonic acid, 2-phenyldyeing regenerated cellulose in even level shades.

9. As newproducts, trisazo dyes having in the form of the free acid the following structural formula:

wherein R represents a naphthalene residue, R represents a coupled residue of an amino naphthol sulphonic acid, R represents hydrogen, an alkyl or alkoxy group, R represents hydrogen or an alkoxygroup, and X represents hydrogen or a $05K group, said trisazo dyes being capable of dyeing regenerated cellulose in even level shades.

10. As new products, trisazo dyes having the following structural formula:

R5 Ru zen:

sents a COOH or $0 11 group, and represents hydrogen or sulphonic group, said trisazo dyes being capable of dyeing regenerated cellulose in even level shades.

11. As new products, trisazo dyes having in v the form of the free acid the following probable structural formula: I v

HIN

wherein R represents a benzene or naphtha lene residue, A represents hydrogen, a COOH group, A representsH or SO H, and m is 1 or 2, said trisazo dyes being capable of dyeing regenerated cellulose in even level shades.

12. As new products, trisazo dyes having in the form T of the ,free acid the following probable structural'formula:1' Y

wherein R represents a benzene or naphthalene residue, R represents a coupled res due offan 'amino-naphthol sulphonio acid, R 1 repthe form of free acid the following structural resents hydrogen, an alkyl or alko xy group,

;R' represents hydrogen or an alkoxy group, r pr hy rog GQOH. .go i SO H J group,;andrepresents hydrogen or'a SQsH' g Ri I-I'u i I= N Y group','saidtrisazo dy'es,-beingcapable of dyeing regenerated cellulose'in even level shades. 13. As new products, trisazo dyes having in formula hydrogen or SO H group, said trisazo dy es beingoapable of dyeing regeneratedcellulose v,inevenlevelshades V d 14. As ew products,trisazo dyes having in i' ng Prob ble the form of free acidthe structural formula:

. i ni tom I wherein R represents a benzene or naphthalene residue, R represents a naphthalene resi-" due, R represents hydrogen, a CH or Egl'OllP, R represents hydrogen, a; ::phenyl,

benzoyl or acetyl group, A represents hydro-1;

gen, a COOH or $0 11 group, and w is 1 012, said trisazo dyes being capable of dyeing regenerated cellulose in even level shades.

: 1 51 As' new products, tri'sazo dyes havingin r the form of free acid'the the form of the free acid "gable formula:

the immerses and the renewin probable structural formula;

wherein R represents a benzene or naphthalene residue, R represents a naphthalene residue, R represents hydrogen, a phenyl,

"benzoyl or acetyl group, A representshydroe I (lOO'H'or'sOgH group, and w is 1 or'2, v. sa'id'trisazo dyes being capable of dyeing'rd generated cellulose'ineven level shadesj 16. As newproducts, trisazo dyes having in structuralfforn ula:

:xwher'ein R represents a benzene or naphthalene residue, R represents a naphthalene resi-.

represents-.;hydr0gen,' a phenyl,

group "JR 8 A, represents hybenzoyl or acetyl group,

drogen, a COOH or $0 11 group, X reprew W i nts hy r gen o a. ;03H?sr P, s 5 r I regenerated cellulosein even level shades.

17 As newproducts, trisazo dyeshavillg structural formula:

I (8on1)z I wherein R2 and R represents a naphthaf ollowing probable :7

due, R represents hydrogen :or"a' -OC H .th brmbfifre a dit e zfe owi p b b e 'lene residue, R representsa benzene or naph= V ;th alene residue, represents H, C OOH or. SQ H group, R vrepres'ents hydrogen, an

'alkyl or alkoxy.groupflt lepresents'hydroq gen,-an arylor acyligroup, Xjrepresents-hydrogen 1or QSOJTIQg rQuP andw is: 1 .0r12', said 1 enerat d ce l se n e el-s a trisazo dyes containing at least two or; v CQ gwups and b s era sp dy ie 18; As new prod'uets'a trisa zo dye'havingin v the following prob saidtrisazo dye being capable of dyeing regenerated cellulose in even level blue shades. 19. As new products, trisazo dyes having in the form of free acid the following probafble structural formula:

R v QN=N N=NR|-OH Rr-N= I group and R represents hydrogen or a phenyl group, said two trisazo dyes being capable of dyeing regenerated cellulose in even level shades. I

23. As new'products, trisazo dyes having 70 in the form of free acid the following structural formula:

BIN on QN=N wherein R represents a naphthalene residue,

said trisazo dye being, capable of dyeing re-' generated cellulose in even-level violet black shades;

21. As new products, t-risazo dyes having in the form of free -acid the tural formula wherein R represents a coupled residue of an amino-na hthol-sulphonic acid, R repre-. sents H (lll or OCH, group, R representsH or OC l-L, group, and X represents H or SO,H group, said trisazo dyes being capable of dyeing regenerated cellulose in even level shades. 1

new products, trisa zo dyes havingin the form ofufree acid the following structural formula: v

wherein R represents hydrogen or a OCH following struc- Wherein R represents a naphthalene residue, R represents a CH or OCH group and X represents hydrogen or sulphonic group, said two trisazo dyes containing at least two SO H groups and being capable of dyeing regenerated cellulose in even level shades.

24:. As new products a trisazo dye having in the form of the free acid the following probable formula:

. OCH: OH mu on QN N N=N said trisazo dye being capable of dyeing re generated cellulose in even level navy blue shades.

25. Asnew'products, trisazo dyes having in the form of free acid the following probable structural formula:

1 wherein R5 represents a benzene residue, R

represents a coupled residue of an amino naphthol sulphonic acid, R represents hydrogen, an alkyl or alkoxy group, R represents hydrogen or an alkyl group, and X represents hydrogen or SO H group, said trisazo dyes being capable of dyeing regenerated cellulose in even level shades.

26. As new products, trisazo dyes having in the form of free acid the following probable structural formula:

wherein R represents a coupled residue of an amino-naphthol-sulphonic acid, R represents hydrogen, an alkyl or alkoxy group, R represents hydrogen or an alkoxy group, R represents hydrogen or alkyl group, and X represents hydrogen or $0 11 group, said trisazo dyes being capable of dyeing regenerated cellulose in even level shades.

27. As new products, trisazo dyes having in the form of free acid the following structural formula.-

I OH

in the form of the free acid the following probable formula:

HnN OH Hols \SOBH said trisazo dye being capable of dyeing regenerated cellulose in even level violet shades.

29. As new products a trisazo dye having in the form of the free acid the following probable formula:

N=NOOH mNOfism SOzH said trisazo dye being capable of dyeing regenerated cellulose in even level deep brown shades.

In testimony whereof I aflix my signature.

RAINALD BRIGHTMAN.

Certificate of Correction Patent No. 1,876,848. September 13, 1932.

RAINALD BRIGHTMAN It is hereby certified that error appears in the printed specification of the abovenumbered patent requiring correction as follows: Page 1, line 6, beginning With the period and the Words This latter strike out all through and including the Word and comma group, in line 20; and line 29, after thereof. insert instead: This latter class of compounds may be represented by the probable formula:

EQNQagNHZ wherein R represents hydrogen, an alkyl or allcoooy group, R represents hydrogen or an alicoxg group and X represents hydrogen or a sulphonz'e group; page 2, line 86, for 60 read 69; page 4, line 90, claim 3, for the misspelled Word akyl read alhg l page 5, line 70, claim 5, for the article a read the; and that the said Letters Patent should be read With these corrections therein that the same may conform to the record of the case in the Patent Office.

Signed and sealed this 22d day of November, A. D. 1932.

[SEAL] M. J. MOORE, Acting Gammissz'oner of Patents. 

